Method of depositing carbon-containing material on a surface of a substrate, structure formed using the method, and system for forming the structure

ABSTRACT

Methods and systems for filling a recess on a surface of a substrate with carbon-containing material are disclosed. Exemplary methods include forming a first carbon layer within the recess, etching a portion of the first carbon layer within the recess, and forming a second carbon layer within the recess. Structures formed using the method or system are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No. 62/937,924, filed on Nov. 20, 2019 in the United States Patent and Trademark Office, the disclosure of which is incorporated herein in its entirety by reference.

FIELD OF INVENTION

The present disclosure generally relates to methods of forming structures suitable for use in the manufacture of electronic devices. More particularly, examples of the disclosure relate to methods of filling gaps with carbon-containing material during the formation of structures.

BACKGROUND OF THE DISCLOSURE

During the manufacture of devices, such as semiconductor devices, it is often desirable to fill features (e.g., trenches or gaps) on the surface of a substrate with insulating or dielectric material. Some techniques to fill features include the deposition of carbon-containing material.

Although use of carbon-containing material to fill features can work well for some applications, filling features using traditional deposition techniques has several shortcomings, particularly as a size of the features to be filled decreases. For example, during deposition of carbon-containing material, voids can form within the deposited material, particularly within gaps. Such voids can remain even after reflowing the deposited material. Further, an undesirably wavy or rough top surface of the deposited carbon-containing material can form. The undesirably wavy or rough top surface can detrimentally affect subsequent processing steps, such as patterning, etching, and/or deposition steps.

As device and feature sizes continue to decrease, it becomes increasingly difficult to apply conventional carbon-containing material deposition techniques to manufacturing processes. Accordingly, improved methods for forming structures, particularly for methods of forming structures that include filling gaps with carbon-containing material, that mitigate void formation in the carbon-containing material and/or that provide a smoother top surface of the carbon-containing material, are desired.

Any discussion, including discussion of problems and solutions, set forth in this section, has been included in this disclosure solely for the purpose of providing a context for the present disclosure, and should not be taken as an admission that any or all of the discussion was known at the time the invention was made or otherwise constitutes prior art.

SUMMARY OF THE DISCLOSURE

Various embodiments of the present disclosure relate to methods of forming structures suitable for use in the formation of electronic devices. While the ways in which various embodiments of the present disclosure address drawbacks of prior methods and structures are discussed in more detail below, in general, exemplary embodiments of the disclosure provide improved methods for filling features on a surface of a substrate with carbon-containing material and/or to forming layers or films comprising carbon.

In accordance with various embodiments of the disclosure, methods of filling a recess on a surface of a substrate are provided. Exemplary methods can include providing a substrate in a reaction space of a reactor, the substrate comprising a surface comprising a recess; forming a first carbon layer within the recess, wherein the first carbon layer can be initially flowable; etching a portion of the first carbon layer within the recess; and forming a second carbon layer within the recess. The second carbon layer can also be initially flowable. Exemplary methods can further include a step of etching a portion of the second carbon layer. Methods can further include forming a third (or top) carbon layer overlying the second carbon layer. The steps of forming the second carbon layer and etching the portion of the second carbon layer can be repeated a number of times prior to the step of forming the third carbon layer. In some cases, the first carbon layer can fill the recess to at least a top surface of the substrate. In such cases, the step of etching a portion of the first carbon layer can include etching the first carbon layer until a surface of the first carbon layer within the recess is below the top surface. In accordance with further examples of the disclosure, the second carbon layer can fill the recess to at least a top surface of the substrate. The step of etching a portion of the second carbon layer can also include etching the second carbon layer until a surface of the second carbon layer within the recess is below the top surface. One or more of the carbon-containing layers can be deposited using a cyclic deposition process, such as a plasma-enhanced cyclic deposition process. A plasma-enhanced cyclic deposition process can include providing a dilution gas, such as argon or helium, to a remote or direct plasma unit for igniting and sustaining a plasma. Exemplary methods can further comprise a treatment step to treat one or more of the carbon layers. A treatment step can include a plasma treatment step—e.g., treatment with species formed from one or more of argon, helium, nitrogen, and hydrogen. Various etching steps can be performed using a plasma-enhanced etch process.

In accordance with yet further exemplary embodiments of the disclosure, a structure is formed, at least in part, according to a method described herein.

In accordance with yet further exemplary embodiments of the disclosure, a system is provided for performing a method and/or for forming a structure as described herein.

These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments having reference to the attached figures; the invention not being limited to any particular embodiment(s) disclosed.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

A more complete understanding of exemplary embodiments of the present disclosure can be derived by referring to the detailed description and claims when considered in connection with the following illustrative figures.

FIG. 1 illustrates a method in accordance with exemplary embodiments of the disclosure.

FIG. 2 illustrates a scanning transmission electron microscopy image of a structure including a carbon layer.

FIG. 3 schematically illustrates structures formed using a method in accordance with examples of the disclosure.

FIG. 4 illustrates scanning transmission electron microscopy images of structures formed in accordance with exemplary embodiments of the disclosure.

FIG. 5 illustrates a system in accordance with exemplary embodiments of the disclosure.

It will be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of illustrated embodiments of the present disclosure.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Although certain embodiments and examples are disclosed below, it will be understood by those in the art that the invention extends beyond the specifically disclosed embodiments and/or uses of the invention and obvious modifications and equivalents thereof. Thus, it is intended that the scope of the invention disclosed should not be limited by the particular disclosed embodiments described below.

The present disclosure generally relates to methods of depositing materials, to methods of forming structures, to structures formed using the methods, and to systems for performing the methods and/or forming the structures. By way of examples, the methods described herein can be used to fill features, such as gaps (e.g., trenches or vias) on a surface of a substrate with material, such as carbon-containing (e.g., dielectric) material. The terms gap and recess can be used interchangeably.

To mitigate void and/or seam formation, the carbon-containing material can be initially flowable and flow within the gap to fill the gap from the bottom upward. Exemplary structures described herein can be used in a variety of applications, including, but not limited to, cell isolation in 3D cross point memory devices, self-aligned vias, dummy gates, reverse tone patterns, PC RAM isolation, cut hard mask, DRAM storage node contact (SNC) isolation, and the like.

In this disclosure, “gas” can refer to material that is a gas at normal temperature and pressure, a vaporized solid and/or a vaporized liquid, and may be constituted by a single gas or a mixture of gases, depending on the context. A gas other than a process gas, i.e., a gas introduced without passing through a gas distribution assembly, such as a showerhead, other gas distribution device, or the like, may be used for, e.g., sealing a reaction space, which includes a seal gas, such as a rare gas. In some cases, such as in the context of deposition of material, the term “precursor” can refer to a compound that participates in the chemical reaction that produces another compound, and particularly to a compound that constitutes a film matrix or a main skeleton of a film, whereas the term “reactant” can refer to a compound, in some cases other than a precursor, that activates a precursor, modifies a precursor, or catalyzes a reaction of a precursor; a reactant may provide an element (such as O, H, N, C) to a film matrix and become a part of the film matrix when, for example, radio frequency (RF) power is applied. In some cases, the terms precursor and reactant can be used interchangeably. The term “inert gas” refers to a gas that does not take part in a chemical reaction to an appreciable extent and/or a gas that excites a precursor when, for example, RF power is applied, but unlike a reactant, it may not become a part of a film matrix to an appreciable extent.

As used herein, the term “substrate” can refer to any underlying material or materials that may be used to form, or upon which, a device, a circuit, or a film may be formed. A substrate can include a bulk material, such as silicon (e.g., single-crystal silicon), other Group IV materials, such as germanium, or compound semiconductor materials, such as GaAs, and can include one or more layers overlying or underlying the bulk material. Further, the substrate can include various features, such as gaps (e.g., recesses or vias), lines or protrusions, such as lines having gaps formed therebetween, and the like formed within or on at least a portion of a layer or bulk material of the substrate. By way of examples, one or more features can have a width of about 10 nm to about 100 nm, a depth or height of about 30 nm to about 1000 nm, and/or an aspect ratio of about 3 to 100 or about 3 to about 20.

In some embodiments, “film” refers to a layer extending in a direction perpendicular to a thickness direction. In some embodiments, “layer” refers to a material having a certain thickness formed on a surface and can be a synonym of a film or a non-film structure. A film or layer may be constituted by a discrete single film or layer having certain characteristics or multiple films or layers, and a boundary between adjacent films or layers may or may not be clear and may or may not be established based on physical, chemical, and/or any other characteristics, formation processes or sequence, and/or functions or purposes of the adjacent films or layers. The layer or film can be continuous—or not.

As used herein, the term “carbon layer” or “carbon-containing material” can refer to a layer whose chemical formula can be represented as including carbon. Layers comprising carbon-containing material can include other elements, such as one or more of nitrogen and hydrogen.

As used herein, the term “structure” can refer to a partially or completely fabricated device structure. By way of examples, a structure can include a substrate with one or more layers and/or features formed thereon.

As used herein, the term “cyclic deposition process” can refer to a vapor deposition process in which deposition cycles, typically a plurality of consecutive deposition cycles, are conducted in a process chamber. Cyclic deposition processes can include cyclic chemical vapor deposition (CVD) and atomic layer deposition processes. A cyclic deposition process can include one or more cycles that include plasma activation of a precursor, a reactant, and/or an inert gas.

As used herein, the term “atomic layer deposition” (ALD) can refer to a vapor deposition process in which deposition cycles, typically a plurality of consecutive deposition cycles, are conducted in a process chamber. Typically, during each cycle, the precursor is chemisorbed to a deposition surface (e.g., a substrate surface or a previously-deposited underlying surface such as material from a previous ALD cycle), forming a monolayer or sub-monolayer that does not readily react with additional precursor (i.e., a self-limiting reaction). Thereafter, a reactant (e.g., another precursor or reaction gas/reactant) may subsequently be introduced into the process chamber for use in converting the chemisorbed precursor to the desired material on the deposition surface. Typically, this reactant is capable of further reaction with the precursor. Further, purging steps may also be utilized during each cycle to remove any excess precursor from the process chamber and/or remove any excess reactant and/or reaction byproducts from the process chamber after conversion of the chemisorbed precursor. Further, the term “atomic layer deposition,” as used herein, is also meant to include processes designated by related terms, such as chemical vapor atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, or organometallic MBE, and chemical beam epitaxy when performed with alternating pulses of precursor composition(s), reactive gas, and purge (e.g., inert carrier) gas. Plasma-enhanced ALD (PEALD) can refer to an ALD process, in which a plasma is applied during one or more of the ALD steps.

In this disclosure, “continuously” refers to without breaking a vacuum, without interruption as a timeline, without any material intervening step, without changing treatment conditions, immediately thereafter, as a next step, or without an intervening discrete physical or chemical structure between two structures other than the two structures in some embodiments and depending on the context.

A flowability (e.g., an initial flowability) can be determined as follows:

TABLE 1 bottom/top ratio (B/T) Flowability  0 < B/T < 1 None  1 ≤ B/T < 1.5 Poor 1.5 ≤ B/T < 2.5 Good 2.5 ≤ B/T < 3.5 Very good 3.5 ≤ B/T     Extremely good where B/T refers to a ratio of thickness of film deposited at a bottom of a recess to thickness of film deposited on a top surface where the recess is formed, before the recess is filled. Typically, the flowability is evaluated using a wide recess having an aspect ratio of about 1 or less, since generally, the higher the aspect ratio of the recess, the higher the B/T ratio becomes. The B/T ratio becomes higher when the aspect ratio of the recess is higher. The flowability is typically evaluated when a film is deposited in a wide recess having an aspect ratio of about 1 or less. As used herein, a “flowable” film or material exhibits good or better flowability.

As set forth in more detail below, flowability of film can be temporarily obtained when a volatile hydrocarbon precursor, for example, is polymerized by a plasma and deposited on a surface of a substrate, wherein the gaseous precursor is activated or fragmented by energy provided by plasma gas discharge, so as to initiate polymerization, and when the resultant polymer material is deposited on the surface of the substrate, the material shows temporarily flowable behavior. When the deposition step is complete, the flowable film is no longer flowable but is solidified, and thus, a separate solidification process may not be employed.

In this disclosure, any two numbers of a variable can constitute a workable range of the variable, and any ranges indicated may include or exclude the endpoints. Additionally, any values of variables indicated (regardless of whether they are indicated with “about” or not) may refer to precise values or approximate values and include equivalents, and may refer to average, median, representative, majority, etc. in some embodiments. Further, in this disclosure, the terms “including,” “constituted by” and “having” can refer independently to “typically or broadly comprising,” “comprising,” “consisting essentially of,” or “consisting of” in some embodiments. In this disclosure, any defined meanings do not necessarily exclude ordinary and customary meanings in some embodiments.

Turning now to the figures, FIG. 1 illustrates a method 100 of filling a recess on a surface of a substrate in accordance with exemplary embodiments of the disclosure. FIG. 2 illustrates problems that may arise during deposition of a carbon layer. FIGS. 3 and 4 illustrate portions of a structure that can form during method 100. FIG. 5 illustrates a reactor system in accordance with examples of the disclosure.

With reference to FIG. 1, method 100 includes the steps of providing a substrate within a reaction space (step 102), forming a first carbon layer (step 104), etching a portion of the first carbon layer within the recess (step 106), and forming a second carbon layer (step 108). As illustrated, method 100 can also include the steps of etching a portion of the second carbon layer (step 110) and forming a third carbon layer (step 112). As used herein, “first carbon layer” can refer to a carbon layer that is deposited before step 106; “second carbon layer” can refer to one or more intermediate carbon layers that are deposited prior to step 112. In other words, structures as described herein can include multiple second carbon layers, which can be formed by repeating steps 108 and 110, as shown via loop 114.

During step 102, a substrate is provided into a reaction chamber of a reactor. In accordance with examples of the disclosure, the reaction chamber can form part of a cyclical deposition reactor, such as an atomic layer deposition (ALD) (e.g., PEALD) reactor or chemical vapor deposition (CVD) (e.g., PECVD) reactor. Various steps of method 100 can be performed within a single reaction chamber or can be performed in multiple reaction chambers, such as reaction chambers of a cluster tool.

During step 102, a substrate can be brought to a desired temperature and/or the reaction chamber can be brought to a desired pressure, such as a temperature and/or pressure suitable during step 104. By way of examples, a temperature (e.g., of a substrate or a substrate support) within a reaction chamber can be between about 20° C. and about 100° C., or less than 100° C. A pressure within the reaction chamber can be from about 200 Pa to about 1,250 Pa.

FIG. 3(a) schematically illustrates a top portion of a substrate 302 having features 304 formed thereon, with gaps 306 formed between features 304. As can be appreciated, a surface 308 of substrate 302 and other structures illustrated herein may be exaggerated to illustrate embodiments of the disclosure. Further, as noted above, substrate 302 can include additional layers and/or features.

During step 104, a first carbon layer 310, illustrated in FIG. 3(b), is deposited on the substrate. Exemplary techniques for depositing first carbon layer 310 on the substrate surface include cyclical deposition processes, such as PECVD, PEALD, or hybrid PECVD/PEALD techniques. For processes including PECVD, a plasma power can be pulsed and/or activated species formed via a plasma can be pulsed to a reaction.

An exemplary cyclic or PEALD process can include the sub steps of exposing the substrate to a precursor, purging the reaction chamber, expositing the substrate to a reactant (e.g., a plasma-activated reactant), purging the reaction chamber, and repeating these steps until an initial desired thickness of the carbon layer is obtained. A temperature within the reaction chamber and/or of a susceptor can be the same or similar as the temperature during step 102. Similarly, the pressure within the reaction chamber can be as described above in connection with step 102. A power applied to electrodes during step 104 (e.g., during a reactant or activated reactant pulse) can range from about 50 W to about 300 W. A frequency of the power can range from about 2.0 MHz to about 27.12 MHz.

Exposing the substrate to a precursor can include providing a precursor represented by the formula C_(x)H_(y)N_(z), where x is a natural number greater than or equal to 2, y is a natural number, and z is zero or a natural number. For example, x can range from about 2 to about 15, y can range from about 4 to about 30, and z can range from about 0 to about 10. The precursor can include a chain or cyclic molecule having two or more carbon atoms and one or more hydrogen atoms, such as molecules represented by the formula above. By way of particular examples, the precursor can be or include one or more aromatic hydrocarbon structures.

A flowrate of the precursor from a precursor source to the reaction chamber can be from about 0.1 slm to about 2.0 slm. A duration of each exposing the substrate to a precursor sub step can be from about 0.1 sec to about 5.0 sec.

The steps of purging the reaction chamber can include flowing an inert gas to the reaction chamber and/or providing a vacuum pressure within the reaction chamber. A flowrate of the purge gas to the reaction chamber can be from about 0.1 slm to about 2.0 slm. A duration of each purging sub step can be from about 0.1 sec to about 5.0 sec.

The sub step of expositing the substrate to a reactant can include providing one or more of an oxygen-containing gas, such as oxygen and N₂O, a hydrogen-containing gas, such as hydrogen, a nitrogen-containing gas, such as nitrogen and N₂O, and/or one or more inert gases, such as argon and/or helium, to the reaction chamber. The reactant may be diluted with a carrier gas, such as nitrogen and/or an inert gas. By way of examples, the reactant gas can include helium.

A flowrate of the reactant (including any carrier gas) from a reactant source to the reaction chamber can be from about 0.1 slm to about 4.0 slm. A duration of each exposing the substrate to a reactant sub step can be from about 0.1 sec to about 0.5 sec.

In accordance with exemplary aspects of the disclosure, an activated species is formed by exposing a reactant gas to radio frequency and/or microwave plasma. A direct plasma and/or a remote plasma can be used to form the activated species. In some cases, the reactant can be continuously flowed to the reaction chamber and the reactant can be periodically activated for a cyclical deposition process. In these cases, an on time for the plasma for each cycle can be from about 0.5 sec to about 10.0 sec.

Step 104 sub steps can be performed a number of times until a desired film thickness is obtained. Further, subsets of sub steps can be repeated prior to proceeding to the next step.

In the case of cyclic CVD, a reactant and a precursor can be introduced into the reaction chamber at the same time. The reactants and/or reaction byproducts can be purged as described herein. Further, hybrid CVD/PECVD-ALD/PEALD processes can be used, wherein a reactant and precursor can react in the gas phase for a period of time and wherein some ALD occurs.

During step 104, the deposited material can initially flow. Thereafter, first carbon layer 310 may become solid.

FIGS. 2 and 3(b) illustrate structures 200 and 314, respectively, which can be formed during step 104. As illustrated, structure 200 can include a void 202 and a wavy surface 204. Similarly, structure 314 includes a void 312 formed within the as-deposited first carbon layer 310. Without further treatment, structures 200 and 314 would include the undesirably wavy surface and could include undesirable seams and/or voids.

In accordance with particular examples of the disclosure, as illustrated in FIG. 3(b), first carbon layer 310 can be deposited until first carbon layer 310 fills recess 306 to at least a top surface 316 of the substrate 302. However, unless otherwise stated, this need not be the case.

During step 106, a portion of the first carbon layer 310 within the recess 306 is etched, as illustrated in FIG. 3(c). In the illustrated case, a portion of first carbon layer 310 is removed, such that a surface 318 of remaining first carbon layer material 322 within recess 306 is below the top surface 316. In the illustrated case, void 312 is opened to form open void 320. This allows open void 320 to be filled using subsequent steps described below.

During step 106, an etchant is flowed to the reaction chamber. Exemplary etchants include oxygen-containing gases, such as oxygen, or hydrogen-containing gases, such as hydrogen. In these cases, the gas include from about 5.0% to about 50.0% oxygen-containing gas or hydrogen-containing gas in an inert gas. In some cases, the etchant can include one or more of oxygen, hydrogen, argon, helium, and nitrogen. A flowrate of the gas (e.g., oxygen-containing gas and any inert gas) can range from about 1.0 slm to about 4.0 slm.

Activated species can be formed from the gas (e.g., oxygen-containing gas or hydrogen-containing gas and any inert gas) using a direct and/or remote plasma. A power applied to electrodes during step 106 can range from about 100 W to about 800 W. A frequency of the power can range from about 2.0 MHz to about 27.12 MHz.

In accordance with various embodiments of the disclosure, a temperature within the reaction chamber during step 106 is less than 100° C. or is between about 20° C. and about 100° C. A pressure within the reaction chamber during step 106 can be from about 200 Pa to about 1,250 Pa.

During step 108, a second carbon layer 324, illustrated in FIG. 3(d), is deposited overlying substrate 302. Exemplary techniques for depositing second carbon layer 324 on the substrate surface include cyclical deposition processes, such as PECVD, PEALD, or hybrid PECVD/PEALD techniques, such as those described above in connection with step 104. A reaction chamber pressure, reaction chamber temperature, and/or plasma power conditions (e.g., power and frequency) during step 108 can be the same or similar to those described above in connection with step 104. Similarly, the same or similar precursors and/or reactants can be used during step 108 as used during step 104. As illustrated, second carbon layer 324 can be deposited until a surface 326 of second carbon layer 324 is above substrate surface 316. As further illustrated, surface 326 may still exhibit an undesirably wavy surface.

During step 110, a portion of the second carbon layer 324 is etched or otherwise removed, as illustrated in FIG. 3(e). In the illustrated case, a portion of second carbon layer 324 is removed, such that a surface 328 of remaining second carbon layer material 330 is above top surface 316 of substrate 302. Further, step 110 can form a substantially planar (non-wavy) surface 328.

In accordance with various embodiments of the disclosure, a temperature within the reaction chamber during step 108 is less than 100° C. or is between about 20° C. and about 100° C. A pressure within the reaction chamber during step 108 can be from about 200 Pa to about 1,250 Pa. A power applied to electrodes during step 108 can range from about 50 W to about 300 W. A frequency of the power can range from about 2.0 MHz to about 27.12 MHz.

As illustrated in FIG. 1, steps 108 and 110 can be repeated a number of times via loop 114 to form structure 332. In some cases, as noted above, at least one instance of step 108 can include depositing the second carbon layer until the second layer fills recess 306 to at least top surface 316. In these cases, at least one occurrence of step 110 can include etching a portion of the second carbon layer until a surface of the second carbon layer within the recess is below the top surface; however, in other cases, the etch/removal step does not remove the second carbon layer to below top surface 316. After the last occurrence of step 110, remaining second carbon layer material 330 is preferably above top surface 316.

With reference to FIG. 1 and FIG. 3(f), during step 112, a third carbon layer 334 can be deposited over remaining second carbon layer material 330. A reaction chamber pressure, reaction chamber temperature, and/or plasma power conditions (e.g., power and frequency) during step 112 can be the same or similar to those described above in connection with steps 104 and 108. Similarly, the same or similar precursors and/or reactants can be used during step 112 as used during steps 104 and 108.

Each of steps 102-104 or sub steps or any combination thereof can be performed within the same reaction chamber. Alternatively, multiple reaction chambers—e.g., of the same cluster tool—can be used for one or more of the steps or sub steps.

Referring again to FIG. 1, one or more of steps 104, 108, and 112 can include a treatment step. The treatment step can include a plasma treatment step. Exemplary plasma treatment steps can include exposing one or more of the first carbon layer, the second carbon layer, and the third carbon layer to species formed using one or more of a direct plasma and a remote plasma. The species can be formed from one or more of argon, helium, nitrogen, and hydrogen (e.g., a combination of argon and helium or a combination of nitrogen and hydrogen). A temperature within a reaction chamber during the species formation for treatment can be less than 100° C. or between about 20° C. and about 100° C. A pressure within a reaction chamber during the species formation for treatment can be from about 200 Pa to about 1,250 Pa. A power applied to electrodes during the species formation for treatment can range from about 100 W to about 800 W. A frequency of the power can range from about 2.0 MHz to about 27.12 MHz. The species formation for treatment step can be formed in the same reaction chamber used for one or more or steps 102-112 or can be a separate reaction chamber, such as another reaction chamber of the same cluster tool.

FIG. 4 illustrates scanning transmission electron microscopy images after step 104 (FIG. 4(a)), after step 106 (FIG. 4(b)), and after step 108 (FIG. 4(c)). In the illustrated examples, a top surface of the second carbon layer is relatively smooth.

FIG. 5 illustrates a reactor system 500 in accordance with exemplary embodiments of the disclosure. Reactor system 500 can be used to perform one or more steps or sub steps as described herein and/or to form one or more structures or portions thereof as described herein.

Reactor system 500 includes a pair of electrically conductive flat-plate electrodes 4, 2 in parallel and facing each other in the interior 11 (reaction zone) of a reaction chamber 3. A plasma can be excited within reaction chamber 3 by applying, for example, HRF power (e.g., 13.56 MHz or 27 MHz) from power source 25 to one electrode (e.g., electrode 4) and electrically grounding the other electrode (e.g., electrode 2). A temperature regulator is provided in a lower stage 2 (the lower electrode), and a temperature of a substrate 1 placed thereon can be kept at a desired temperature. Electrode 4 can serve as a gas distribution device, such as a shower plate. Reactant gas, dilution gas, if any, precursor gas, and/or etchant can be introduced into reaction chamber 3 using one or more of a gas line 20, a gas line 21, and a gas line 22, respectively, and through the shower plate 4. Although illustrated with three gas lines, reactor system 500 can include any suitable number of gas lines.

In reaction chamber 3, a circular duct 13 with an exhaust line 7 is provided, through which gas in the interior 11 of the reaction chamber 3 can be exhausted. Additionally, a transfer chamber 5, disposed below the reaction chamber 3, is provided with a seal gas line 24 to introduce seal gas into the interior 11 of the reaction chamber 3 via the interior 16 (transfer zone) of the transfer chamber 5, wherein a separation plate 14 for separating the reaction zone and the transfer zone is provided (a gate valve through which a wafer is transferred into or from the transfer chamber 5 is omitted from this figure). The transfer chamber is also provided with an exhaust line 6. In some embodiments, the deposition, etch and/or surface treatment steps are performed in the same reaction space, so that two or more (e.g., all) of the steps can continuously be conducted without exposing the substrate to air or other oxygen-containing atmosphere.

In some embodiments, continuous flow of a carrier gas to reaction chamber 3 can be accomplished using a flow-pass system (FPS), wherein a carrier gas line is provided with a detour line having a precursor reservoir (bottle), and the main line and the detour line are switched, wherein when only a carrier gas is intended to be fed to a reaction chamber, the detour line is closed, whereas when both the carrier gas and a precursor gas are intended to be fed to the reaction chamber, the main line is closed and the carrier gas flows through the detour line and flows out from the bottle together with the precursor gas. In this way, the carrier gas can continuously flow into the reaction chamber, and can carry the precursor gas in pulses by switching between the main line and the detour line, without substantially fluctuating pressure of the reaction chamber.

A skilled artisan will appreciate that the apparatus includes one or more controller(s) 26 programmed or otherwise configured to cause one or more method steps as described herein to be conducted. The controller(s) are communicated with the various power sources, heating systems, pumps, robotics and gas flow controllers, or valves of the reactor, as will be appreciated by the skilled artisan.

In some embodiments, a dual chamber reactor (two sections or compartments for processing wafers disposed close to each other) can be used, wherein a reactant gas and a noble gas can be supplied through a shared line, whereas a precursor gas is supplied through unshared lines.

The example embodiments of the disclosure described above do not limit the scope of the invention, since these embodiments are merely examples of the embodiments of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the disclosure, in addition to those shown and described herein, such as alternative useful combinations of the elements described, may become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims. 

What is claimed is:
 1. A method of filling a recess on a surface of a substrate, the method comprising the steps of: providing a substrate in a reaction space of a reactor, the substrate comprising a surface comprising a recess; forming a first carbon layer within the recess, wherein the first carbon layer is initially flowable; etching a portion of the first carbon layer within the recess; and forming a second carbon layer within the recess.
 2. The method of claim 1, wherein the second carbon layer is initially flowable.
 3. The method of claim 2, further comprising a step of etching a portion of the second carbon layer.
 4. The method of claim 1, further comprising a step of forming a third carbon layer overlying the second carbon layer.
 5. The method of claim 3, further comprising repeating the steps of forming the second carbon layer and etching the portion of the second carbon layer.
 6. The method of claim 1, wherein the first carbon layer fills the recess to at least a top surface of the substrate.
 7. The method of claim 1, wherein the step of etching a portion of the first carbon layer comprises etching the first carbon layer until a surface of the first carbon layer within the recess is below the top surface.
 8. The method of claim 1, wherein the second carbon layer fills the recess to at least a top surface of the substrate.
 9. The method of claim 1, wherein the step of etching a portion of the second carbon layer comprises etching the second carbon layer until a surface of the second carbon layer within the recess is below the top surface.
 10. The method of claim 1, wherein the first carbon layer is formed using one or more of plasma-enhanced chemical vapor deposition, plasma-enhanced atomic layer deposition, and a hybrid chemical vapor deposition and atomic layer deposition process.
 11. The method of claim 1, wherein the second carbon layer is formed using one or more of plasma-enhanced chemical vapor deposition, plasma-enhanced atomic layer deposition, and a hybrid chemical vapor deposition and atomic layer deposition process.
 12. The method of claim 4, wherein the third carbon layer is formed using one or more of plasma-enhanced chemical vapor deposition, plasma-enhanced atomic layer deposition, and a hybrid chemical vapor deposition and atomic layer deposition process.
 13. The method of claim 10, wherein one or more of plasma-enhanced chemical vapor deposition, plasma-enhanced atomic layer deposition, and a hybrid chemical vapor deposition and atomic layer deposition process comprise providing argon or helium dilution gas for igniting and sustaining the plasma.
 14. The method of claim 4, wherein one or more of the steps of forming the first carbon layer, forming the second carbon layer, and forming the third carbon layer comprise providing a precursor represented by the formula C_(x)H_(y)N_(z), where x is a natural number greater than or equal to 2, y is a natural number, and z is zero or a natural number.
 15. The method of claim 4, wherein one or more of the steps of forming the first carbon layer, forming the second carbon layer, and forming the third carbon layer comprise providing a precursor comprising a chain or cyclic molecule having two or more carbon atoms and one or more hydrogen atoms.
 16. The method of claim 4, wherein a temperature within the reaction space during one or more of the steps of forming the first carbon layer, forming the second carbon layer, and forming the third carbon layer is less than 100° C.
 17. The method of claim 4, wherein one or more of the steps of forming the first carbon layer, forming the second carbon layer, and forming the third carbon layer comprise a treatment step.
 18. The method of claim 17, wherein the treatment step comprises a plasma treatment step.
 19. The method of claim 18, wherein the plasma treatment step comprises exposing one or more of the first carbon layer, the second carbon layer, and the third carbon layer to species formed using one or more of a direct plasma and a remote plasma.
 20. The method of claim 18, wherein the species are formed from one or more of argon, helium, nitrogen, and hydrogen.
 21. The method of claim 3, wherein one or more of the steps of etching the portion of the first carbon layer and etching the portion of the second carbon layer comprise a plasma-enhanced etch process.
 22. The method of claim 21, wherein an etchant used during one or more of the steps of etching the portion of the first carbon layer and etching the portion of the second carbon layer comprises supplying one or more of oxygen, hydrogen, argon, helium, nitrogen to the reaction space.
 23. A structure formed according to the method of claim
 1. 24. A system for performing the steps of claim
 1. 